Process for producing a water - repellent finish fast to washing on fibrous materials



United States Patent Office US. Cl. 117135.5 10 Claims ABSTRACT OF THE DISCLOSURE A water repellent finish fast to Washing can be produced on fibrous materials, such as cellulosic fibers, without undesired deposit of waxy products on the fibrous material or on the apparatus, by treatment in an aqueous bath and subsequent heat treatment, if desired or required after an intermediate drying, by using a bath which contains:

(a) a methylolaminotriazine esterified with higher fatty acids or etherified with higher alcohols (b) a hydrophobic wax-like substance (c) a surface-active product containing at least one higher aliphatic hydrocarbon residue with at least 16 carbon atoms, linked with nitrogen, and polyglycol residues with an average of at least 10 groups (d) a protective colloid and (e) a curing catalyst,

the ratio (a):(b) being from 2:3 to 9:1, and the preparation containing 2 to 10% of the components (a)+(b) and 0.05 to of component (d).

DETAILED DESCRIPTION As component (a) there are used, for example, derivatives of formoguanamine, acetoguanamine or benzoguanamine, and preferably those of melamine. Methylol groups of these compounds are esterified with higher fatty acids containing at least 14 carbon atoms, or etherified with (preferably aliphatic) alcohols containing at least 14 carbon atoms. In addition to the methylol groups modified in this manner, the triazine compounds further contain advantageously methylol groups etherified with lower alkanols, such as butanol, isopropanol or especially methanol. As a rule it is advantageous for the methylol groups present to be further substituted in the indicated manner to an extent of at least 75%, in fact to be esterified with higher fatty acids or etherified with higher alcohols to an extent of 20 to 50%. As examples of higher acyl radicals there may be mentioned above all those of the fatty acids containing 16 to 18 carbon atoms: the radicals need not be identical, and in additional to alkyl groups with 15 and/ or 17 carbon atoms they may also con- 3,508,958 Patented Apr. 28, 1970 tain higher alkyl groups. The esters accessible from methylolmelamine ether and stearic acid are especially suitable, above all those which have been obtained by reacting highly methylated methylolmelamines with stearic acid, for which purpose so-called commercial stearic acid can be used instead of pure stearic acid with practically identical results. As an example of a higher alcohol n-octadecanol may be mentioned.

As substance (b) there may be used the known waxlike hydrophobizing agents, for example beeswax and polyethylene and especially parafiin waxes whose melting point is advantageously from 45 to C. The substance (b) is advantageously soluble in the substance (a).

According to this invention there are used as substance (c) compounds containing higher aliphatic hydrocarbon residues linked with nitrogen, of which at least 20% should contain at least 20 carbon atoms, and polyglycol residues with an average of at least 10 groups. There may be used products containing a uniform, preferably saturated aliphatic hydrocarbon residue. However, the advantageous effect of these compounds materializes also when mixtures of such nitrogenous polyglycols are used that contain only at least 20%, preferably at least 60%, of hydrocarbon residues with 20 or more than 20 carbon atoms and in addition hydrocarbon residues with 18 or fewer than 18, for example 16, carbon atoms. The use of such mixtures has the advantage that the alkylamine mixtures required as starting materials are easier to manufacture than the uniform alkylamines. Otherwise, for example, there are used the polyglycol compounds accessible by reacting N- monoalkylethyleneor -propylene-diamines and ethylene oxide and above all the polyglycol compounds obtained from N-monoalkylamines and ethylene oxide, and in this connection, too, the alkyl radicals contain to an extent of at least 20% at least 20, preferably 20 or 22, carbon atoms in a straight chain. The average number of groups per module is at least 10 and advantageously from 20 to 40. Those compounds are preferred which contain as l I o o-0- groups exclusively -CH -OH O groups. However, in their stead there may also be presentadvantageously only to a minor extent-the groups formed on reaction with propylene oxide or styrene oxide. The polyglycol compounds obtained in this manner from the amines contain tertiary nitrogen atoms and may be quaternated, for example with dimethylsulphate, 0r preferably with quaternating agents that give rise to quaternary compounds containing a halogen anion such as Clor Br-, for example with alkylchlorides or alkylbromides, chloracetic acid amide or bromacetic acid amide or especially advantageously with chlorethanol [ethylene chlorohydrin], benzylchloride or epichlorohydrin. These quaternary ammonium salts may be used as component (c) in the same manner as the un-quatemated compounds.

As is shown above, there may be specially mentioned the products of formula in which R represents a linear aliphatic hydrocarbon residue containing at least 16 carbon atoms, and m and n are whole numbers, at least 20% of the R-N residues containing at least 20 carbon atoms and the sum m+n being from 20 to 40, as well as the corresponding quaternary ammonium compounds.

As protective colloid (d) there may be used, for example, hydroxyethylcellulose, the sodium. salt of carboxymethylcellulose, polyethyleneglycol, polyacrylamide, polyvinylpyrrolidone, a carboxyvinyl polymer and more especially polyvinyl alcohol. Preferred use is made of a polyvinyl alcohol of medium to high viscosity, having a degree of saponification of over 86%. Its 5% aqueous solutions have at 25 C. a viscosity of 40 to 80 centipoises, measured in a rotary viscosimeter, with the radii of the measuring body and of the measuring beaker being at a ratio of 0.96.

As curing catalysts (e) for the methylol compound (a) there may be used the known acid or potentially acid aminoplast curing agents, for example ammonium salts of strong acids such as ammonium thiocyanate or chloride; zinc nitrate, chloride or fluoborate; magnesium chloride, hydrochloric acid, phosphoric acid or formic acid. Particularly good results are obtained with aluminum salts, for example with aluminum chloride or sulphate.

The baths to be used according to this invention may be prepared in the usual manner. It is advantageous first to prepare an emulsion containing the indicated proportions of substances (a) to (d), but at a concentration higher than the actual working concentration. Such emu1- sions, which have good keeping properties, are characterized in that they contain:

(a) a methylolaminoniazine esterified with higher fatty acids or etherified with higher alcohols (b) a hydrophobic wax-like substance (c) a surface-active product containing higher aliphatic hydrocarbon residues with at least 16 carbon atoms, linked with nitrogen, and polyglycol residues with an average of at least groups (d) a protective colloid the ratio (a) :(b) being from 2:3 to 9:1, the preparation advantageously containing 20 to 50% of (a)+(b), 1.5 to 20% of component (c) and 0.5 to 5.0% of component (d).

According to an advantageous manner of manufacturing the emulsions the following procedure is adopted: First, the substances (c) and (d), which give a true or colloidal solution in water, and, to prevent too low a pH value and therewith premature curing, a small quantity of an amine (for example morpholine, methylmorpholine, hydroxyethylrnorpholine, diethylethanolamine, methyldiethanolamine, ethyldiethanolamine, triethanolamine or dimethylethanolamine) are introduced into the requisite quantity of water and then, at an elevated temperature, the components (a) and (b) are added successively or preferably simultaneously in the form of a heated melt. With the aid of an efficient stirrer or another suitable device it must be ensured that homogenization of the corresponding two-phase system takes place immediately. The necessary heat is advantageously supplied by choosing the emulsioning temperature close to the boiling point without, however, actuall reaching it. During the emulsioning operation or especially after it, further substances, for example anti-foaming agents, may be added.

For use the emulsion is diluted with cold or warm water and the curing catalyst is added. The treatment of the fibrous material, for example cotton or fibres from regenerated cellulose, with the baths of the composition defined above can be carried out at room temperature or at a slightly higher temperature with the conventional devices, advantageously on a padder. The weight increase is advantageously within the range from 60 to The fibrous material impregnated in the manner described above may then be dried before it is subjected to a heat treatment, for example at to C., for 20 minutes to 1 minute.

The finishes obtained by the present process render the fibrous material water-repellant and are fast to washing. The requisite baths of the composition defined above have the advantage that even when large batches of material are treated, no Waxy products deposit on the fabric or on the apparatus, especially on the padding rollers.

Manufacturing Instruction A In the following description of the manufacture of 500 g. of an emulsion the data from the following Table II should be inserted.

In a heatable vessel equipped with a propeller stirrer, whose speed can be infinitely varied, v grams of polyvinyl alcohol powder (V) are dissolved with moderate stirring first at 20 to 25 C. and then at 70 C. in 142.5:5 g. of water (the quantity of water to be added depends on the content of emulsifier). Then a grams of amine (A) and e grams of emulsifier (E) are added and dissolved. Then, beginning at 85 C., a homogeneous melt heated to 105 C. from m grams of a condensation product M (prepared as described below) and p grams of paraflin wax (P) is then poured into the aqueous emulsifier solution, and the whole is stirred at increasing speed until a colloidal emulsion has formed; during this it is ensured by regulation of the external heating that the emulsion does not come to the boil. Then, 96.75 g. of water at 70 C. and 3 g. of an anti-foaming agent based on silicone in disperse form are added with slow stirring. The whole is once more stirred at high speed and a finely disperse emulsion is obtained which is cooled to room temperature in running water but without being stirred. The emulsion obtained in this manner may be diluted with cold or warmv water and reveals the properties mentioned in the following Examples 1 to 12.

The condensation products M (esterified melamine resins M (I) to M (III), etherified melamine resins M (IV) to M (VI)) are manufactured as follows:

M (I): 324 parts (1 mol) of finely powdered hexamethylolmelamine are stirred into 2000 parts by volume of methanol containing 100 parts by volume of hydrochloric acid of 30% strength. After 10 minutes the methylol compound has dissolved. The solution is im-' mediately stirred with about 160 parts of anhydrous sodium carbonate until it gives a neutral litmus reaction. The precipitated salt is filtered OH and the solution evaporated under vacuum to a syrup of at least 98% strength. The salt which has now additionally settled out is removed by filtration With heating. 100 parts of this methylolmelamine methyl ether are heated with 130 parts of stearic acid in a vacuum of 10 to 20 mm. Hg at to 200 C. until the acid number is 5 to 8.

M (II): 390 grams (1 mol) of the methylolmelamine methyl ether described above under M (I) are heated with 270 g. (1 mol) of commercial stearic acid in a vacuum of 25 to 30 mm. Hg at to 200 C. until the acid number is 2 to 3, which is the case after 3 hours heating.

M (III): 390 grams (1 mol) of the methylolmelamine methyl ether described above under M (I) are heated with 242 g. (1 mol) of myristic acid in a vacuum of 25 to 30 mm. Hg pressure at 195 to 200 C. until the acid number is 2 to 3.

M (IV): 195 grams /z mol) of the methylolmelamine methyl ether described above under M (I) are stirred and heated with 155 g. of a synthetic arachic alcohol in a vacuum of 30 to 35 mm. Hg pressure for 4 hours at 195 to 200 C. After cooling, a viscid product is obtained which gives a clear solution in benzene.

M (V): 250 grams /2 mol) of a 75% butanolic solution of a hexamethylolmelamine butyl ether containing about 2 to 3 butyl groups are heated with 155 g. of a synthetic arachic alcohol in a vacuum of 30 mm. Hg pressure for 1 hour at 120 C., during which butanol distills off. The whole is then heated for another 8 hours and after cooling, a pale yellow, viscid product is obtained which gives a clear solution in benzene.

M (VI): 195 grams /2 mol) of the methylolmelamine methyl ether described above under M (I) are stirred and heated with 105 g. /2 mol) of myristic alcohol in a vacuum of 30 to 35 mm. Hg pressure for 6 hours at 195 to 200 C. The resulting almost colourless, highly viscous mass gives a clear solution in benzene and paraffin wax.

Manufacturing Instruction B In the flolowing description of the manufacture of 50 0 g. of an emulsion the data from the following Table III should be inserted.

In a heatable vessel with propeller mixer as described under (A), v grams of polyvinyl alcohol powder (V) are dissolved with moderate stirring at first at 20 to 25 C. and then at 70 C. in 142.5 g. of water. Then 0.25 g. of dimethylethanolamine is added. Then, beginning at 85 C., a homogeneous melt at 100 to 105 C. from 112.5 g. of an ester M (I) as described above under (A), 112.5 g. of paraffin wax melting at 60 C. and e grams of emulsifier (E) are poured into the aqueous protective colloid solution and the whole is stirred at an increasing speed until an emulsion has formed; by regulating the external heating it is ensured that the emulsion does not come to the boil. Then 71.75 g./46.75 g./2l.75 g. of water heated at 70 C. (the amount of water to be added depends on the content of emulsifier) and 3 g. of an anti-foaming agent based on silicone in disperse form are added with slow stirring. The whole is then once more stirred at high speed and a finely disperse colloidal emulsion is obtained which is cooled to room temperature in running water of C., but without stirring. This emulsion can be stirred and diluted with cold or warm water and reveals the properties described in the following Examples 13 to 17.

Manufacturing Instruction C In the following description of the manufacture of 500 g. of an emulsion the data from the following Table IV should be inserted.

In a heatable vessel with propeller mixer, whose speed can be infinitely varied, v grams of the protective colloid powder (V) are dissolved with moderate stirring first at to C. and then at 70 C. in 142.5 g. of water. Then a grams of amine (A) and 2 grams of emulsifier (E), and an adduct from mols of ethylene oxide with 1 mol of a mixture of 10% of stearylamine, 55% of arachidylamine and of behenylamine are added and dissolved. Then beginning at 85 C., this aqueous emulsifier solution is mixed with a homogeneous melt at about 105 C. from m grams of an ether M (I) from methylolmelamine methyl ether and stearic acid, prepared as described in Manufacturing Instruction A, and p grams of paraffin wax P, b grams of beeswax B and from p0 grams of polyethylene P0, and the whole is stirred at an increasing speed until a colloidal emulsion has formed, while ensuring by regulation of the external heating that the emulsion does not rise to the boil. Then 93 g. of water at 70 C. and 3 g. of an anti-foaming agent based on silicone in disperse form are slowly stirred in. The whole is once more vigorously stirred at high speed and a finely disperse emulsion is obtained which is first adjusted with a small quantity of water at 70 C. to a weight of 500 g. and then cooled to room temperature in running Water but without stirring. The emulsion prepared in this manner can be diluted with cold or warm water and reveals the properties described in the following Examples 18 to 28.

Manufacturing Instruction D In the following description of the manufacture of 500 g. of an emulsion the data from the following Table V should be inserted.

In a heatable vessel with propeller mixer, whose speed can be infinitely varied, v grams of the protective colloid powder V are dissolved with moderate stirring first at 20 to 25 C. and then at 70 C.'in 142.5 g. of water. Then a grams of amine (A) and e grams of emulsifier E are added and dissolved. Beginning at C., a homogeneous melt of about C., from m grams of one of the melamine resins M (I) to M (VI) (whose manufacture has been described in Manufacturing Instruction A) and from p gram of paraffin wax P is poured into the aqueous emulsifier solution and the Whole is stirred at an increasing speed until a colloidal emulsion has formed, while ensuring by regulation of the external heating that the emulsion does not rise to the boil. Then 94.5 g. of water at 70 C. and 3 g. of an anti-foaming agent based on silicone in finely disperse form are slowly stirred in. The whole is once more stirred at high speed and forms a finely disperse emulsion which first is adjusted with a small quantity of water at 60 to 70 C. to a Weight of 500 g. and then cooled to room temperature in running Water but without stirring. The resulting emulsion can be diluted with cold or warm water and possesses the properties described in the following Examples 29 to 35.

EXAMPLE 1 grams of an emulsion prepared according to Instruction A and Table II, Example 1, are diluted with water at room temperature with addition of hydrochloric acid to reach a pH value of 5.0 so that after addition of 24 g. of a 20% aluminum sulphate solution 1 litre of an impregnating bath is obtained, which is poured into the vat of a three-roller padder. A viscose crepe fabric dyed black is passed through the padder, and takes up 60% of the impregnating liquor. The fabric is dried at 80 C. and then hardened for 5 minutes at C. whereupon it displays a water-repellent finish. Neither the fabric nor the padder rollers are dirtied by deposits. To test this, the fabric, instead of being run through the padder only once, may be caused to circulate continuously for one hour as an endless belt of 3 m. length at a speed of 6 m./minute, after which neither on the fabric nor on the rollers any appreciable deposits can be observed. Such dirtying occurs, however, when instead of the substance (c) according to this invention, for example, surface-active adducts from ethylene oxide with higher alcohols or with fatty amines containing exclusively fewer than 20 carbon atoms are used for making the emulsion.

The degree of dirtying of the rollers can be evaluated according to the following Table I proportionally to the number of Ss, the total number of all Ss indicating the degree of dirtying of the padder.

TABLE I Padder:

Top roller S S S SS SS SS SSS Middle roller S S S SS SS SS SSS SSS SSS Bottornroller S S S SS SS SS SSS SSS Degree ofdirtying 0 1 2 3 4 5 6 7 8 9 TABLE II Example N0 MANUFACTURING INSTRUCTION A (I) Emulsion contains- Polyvinyl alcohol:

Highly viscous, 45:1;5 Saponification, 87-89%. Highly viscous, 60i5 Saponiflcation, 9899% (A) Triethanolamine Viscosity of a 4% aqueous solution at 20 C. in centipoises.

TABLE III 1 Viscosity of a 4% aqueous solution at 20 C. in centipoises.

TABLE IV MANUFACTURING INSTRUCTION c Example No TABLE V Example No 29 30 MANUFACTURING INSTRUCTION D (l) Emulsion contains (V) Polyvinylalcohol:

highly viscous, 4&5 1 Degree of snponiflcation, 8789%. Hydroxyethylcellulose 1 ii (A) Dimethylethanolamine a (E) Addutrlrt from 30 mols of ethylene oxide wit 1 mol of a mixture of 10% stearylamine,

55% arachidylamine and 96% behenylamine e= 1 mol of a mixture of 25% hexadocylamine, 70% stearylamine and octadeeenylaminen e 1 mol of a mixture of 90% hexadecyla mine, 6% octadecylamine and 4% octadeeenylarnine (M) Melamine resin:

2.5 112.5 112.5 (IDImpregnating cotton serge:

G/l. emulsion 120 120 120 120 120 120 120 G/l. sulphate 4.8 4.8 4.8 4.s 4.8 4.8 4.3 Spray test:

Specimen unwashed, percent H2O 3. 1 3. 2 5. 1 6. 2 4. 6 3. 2 Washed at the boil, percent H" 3.1 3.0 5. 9 5. l 4. 4 2. 6 5. 7 (III) Padding test: Degree of dirtying 2 2 3 4 0 0 3 (IV) Fabric web:

1 3%.:: 1:333:31:::::::::::::: i l H 0 a g g g TABLE VI groups comprising a monoalkylamine with at least 16 Example No 3s 37 as 39 40 Carbon atoms- MAWFACTUEINGINSTRUCTIONC 3. A process according to claim 1, which comprises (1) Example 22; using as component (c) a surface-active product con- (11) 11 55 15322 c o Serge. -l 120 120 190 120 120 taining higher aliphatic hydrocarbon radicals linked with g f if; nitrogen, of which at least 20% contain at least 20 carbon 2 4 atoms, and polyglycol radicals containing on an average n-nltrate... 5. 4 Mg-Chloride 5.4 at least 10 S ZIlfllil;ObOI'Bte- I I a 8S 1 S peeimenunwashed 3. 5 3.4 4 1 3.8 4. 5 C-CO Specimenwashed 6.6 3.3 3 9 3.4 4.4 IIfiiglding tlest: Degree of dirtying 0 0 1 2 1 g p re 0} 0 g g g 4. A process according to claim 1, which comprises y using as component: I claim: (0) a surface-active compound selected from the group 1. A process for producing a water-repellent finish consisting of acompound of the formula fast to Washing on fibrous materials, which comprises treating the fibrous material in an aqueous bath contain- CH2CH2 O7H ing: R N m (a) a member selected from the group consisting of OH CH H a methylolaminotriazine esterified with fatty acids 2- jn containing at least 14 carbon atoms and a methyli n which re res nts olaminotriazine etherified with fatty alcohols conradical i g g ggg g ggjgg gg gg ggg tammg at least i Garbo? atoms m and n each is a whole number, at least 20% of (b) hydrophoblc Wax-Ilka, Substance Whose meltmg the RN radicals contain at least 20 carbon atoms, pomt 1S betwfiefl 45 and 70 and the sum m+n is from 20 to 80, and the corre- (c) a surface-active product containing higher aliphatic spending quaternary ammonium compound hydrocarbon radicals with at least 16 carbon atoms, A process according to c1 aim 1 which cmprises hnked i 3' Polyglycol radlcals wlth using as component (a) a methylolmelamine methyl ether an avera=e O at east stearic acid ester, as component:

(l) o (b) a hydrophobic, wax-like substance whose melting I l point is between 45 and 70 C. and which is soluble groups in component (a), and as component (d) a protective colloid and (c) a surface-active compound selected from the group (e) a curing catalyst, consisting of a compound of the formula the ratio (a):(b) being from 2:3 to 9:1, and the preparation containing 2 to 10% of the components (a)+(b), (CHr-CHrO7-H 0.15 to 3.2% of component (c) and 0.05 to 5% of component (d); drying and heat hardening the impregnated textiles. CHPCHPO/n H 2. A process according to claim 1, Which comprises using as component (c) a surfac? active product indwhilch R represents a hnear aliphatic hydrocarbon tainmg a polyglycol compound wlth an average of at ra ica containing at least 16 carbon atoms, and m least 10 and n each is a whole number, at least 20% of the I I RN radicals contain atleast 20 carbon atoms, c c o and the sum mi-i-n is from 20 to 80, and the correl spending quaternary ammonium compounds.

1 1 6. A process according to claim 1, which comprises using an component:

(a) a methylolmelamine methyl ether stearic acid ester,

as component (b) paraflin wax, and as component (c) a surface-active product containing higher aliphatic hydrocarbon radicals linked with nitrogen, of which at least 20% contain at least 20 carbon atoms, and polyglycol radicals containing on an average at least 10 groups. 7. A process according to claim 1, which comprises using as component:

(a) a methylolmelamine methyl ether stearic acid ester,

as component (b) paraflin wax, as component a surface-active product containing higher aliphatic hydrocarbon radicals linked with nitrogen, of which at least 20% contain at least 20 carbon atoms, and polyglycol radicals containing on an average at least groups, and as component (d) polyvinyl alcohol.

8. A process according to claim I, which comprises treating the fibrous material in an aqueous bath containmg:

(a) a methylolmelamine methyl ether stearic acid ester (b) paraffin wax (c) a surface-active product containing higher aliphatic hydrocarbon radicals linked with nitrogen, of which at least 20% contain at least 20 carbon atoms, and polyglycol radicals containing on an average at least 10 groups,

(d) polyvinyl alcohol and (e) an aluminum salt, the ratio (a):(b) being from 9:11 to 7:3 and the preparation containing 2 to 10% of the components (a)+(b),

12 0.2 to 2.0% of component (c) and 0.05 to 5% of component (d).

9. A process according to claim 1, which comprises treating the fibrous material in an aqueous bath containmg:

(a) a polymethylolmelarnine-polymethyl ether stearic acid ester,

(b) parafiin wax,

(c) an adduct from 30 mole of ethylene oxide with 1 mol of a mixture of 10% stearylamine, of arachidylamine and 35% of behenylamine,

(d) polyvinyl alcohol and (e) aluminum sulfate, the ratio (a):(b) being from 9:11 to 7:3 and the preparation containing 2 to 10% of the components (aH-(b), 0.2 to 2.0% of component (c) and 0.05 to 5% of component (d).

10. A process according to claim 1, which comprises treating the fibrous material in an aqueous bath containmg:

(a) a polymethylolmelamine-polymethyl ether stearic acid ester (b) parafiin wax (c) an adduct from 30 mols of ethylene oxide with 1 mol of a mixture from 25% of hexadecylamine, of octadecylamine and 5% of octadecenylamine (d) hydroxyethylcellulose and (e) aluminum sulfate, the ratio (a):(b) being from 9:11 to 7:3 and the preparation containing 2 to 10% of the components (a)-|-(b), 0.2 to 2.0% of component (c) and 0.05 to 5% of component ((1).

References Cited UNITED STATES PATENTS 2,357,273 8/ 1944 Thurston 26067.6 X 2,371,892 3/1945 Hood 26067.6 2,491,249 12/ 1949 Cathers et al 26029.4 2,509,174 5/1950 Scott et a1 117-161 2,763,649 9/1956 Albrecht et a1. 1l7l39.4 X 2,971,930 2/1961 Glade 117-1355 X WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US. Cl. X.K 

